Method of making pressure-sensitive adhesive sheeting



' July 26, 1949.

W. J. MOHR METHOD OF MAKING PRESSURE-SENSITIVE ADHESIVE SHEETING Filed June l2, 1945 h If e???r v07' @mu/Www? Patented July 26,1949

or' lMAKING PRESSURE-SENSITIVE rADHESIVE sHEE'rrNG Wilfred J'. Mohr, vDearbornlTow-nship, Wayne` County, Mich.,y assignor toMinnesota Mining &

Manufacturing Company, St., corporation of Delaware Application J une 12,

Y This invention relatestcthe art of making pressure-sensitive adhesive sheets or tapes.

-In the manufacture lof normally tacky andy pressure-sensitive adhesive sheets or tape, such as thewell-known maskingtape; thewater-insoluble pressure-sensitive adhesive is customarily coatedon the 'backing asa solution in a volatile organic solvent, followed by heating to remove the solvent and thus form an aggressively tacky but eucohesive pressure-sensitive adhesive coating.` By. eucohesiveY it is meant ,that the adhesive coating. is'more cohesive vthan adhesive such that offsetting or transferof adhesive material does notresult when the tape -is unwound from rolls or removed from smooth surfaces -to which temporarily applied, and can behandled without ltransfer-of I adhesiveA material to the fingers.l l

VIn the case of certain aqueous dispersions of water-insoluble pressure-sensitive adhesives, simple drying from anexposedsurface of .a coating of thedispersion has .been found to cause a. reduction in tackinessor arlvhesiorivalue of` the dried surface. over the ,value obtainableon coating thesame adhesive composition from an organic solvent.y This eiect is apparently caused by migration lof water-soluble or water-carried dispersing agents, hydrophilic colloidal agglutinants, and the like, which are initially present` in the aqueous phase, to `the evaporative surface, where they are ldepositedin a non-tacky surface lm on evaporation'of the water. An added difficulty, particularly in the manufacture of transparent` adhesive sheets or tape, is thel bubbling or blisteringencountered when dryingf the adhesive dispersion at elevated temperatures.` and which results in reduced transparency. s

I have now found'that it is possible to apply desirably thick films of aqueous dispersione of water-insoluble normally tacky pressure-sensitive adhesives to certain'tape 'backings in :such a way as to provide entirely satisfactory aggressively and stably tacky pressure-sensitive adhesive surfaces without the `formation of vadhe-v sion-masking surface residues'or films. In accomplishing this novel result; I apply the water-- dispersed adhesive'vas an intercalatedlayer between two moisture-permeable backing sheets, remove the water from'the interior ofthe composite through the backing members by evapora- 50` tion, and separate the two adhesive sheets 1thus `Paul, Minn., a.

1945, Serial No. 599,086

methods of'V 4coatingland drying. A'For example;`

tain a normally tacky pressure-sensitive adhesives formed by splitting the adhesive layer atzits. Y

approximate center. Y y t By coating the adhesive between two backings,

I am also enabled to prevent dusting of :the

adhesive surface, stickingY of the adhesive to other-` z surfaces lsuch as Vdrying drums, racks, etc., oxidation of the surface during drying atoelevated. temperatures in contact with air, and other diniculties, attendant upon .the use of the customary I may use a plurality of steam drums for apply-H ing heat to the composite web, without allowing, contact `of the adhesive with the druzmsurfaces;y

ObjectsA of my invention are thereforeto ,ob,

surface from a water-dispersed water-insoluble normally tacky adhesivecontaining water-solu-` ble dispersing agents'and protective colloids; tof obtain a pressure-sensitive adhesive coated sheet` or `tape by the use of water-dispersed adhesive; to l obtain a pressure-'sensitive adhesive L., coatedsheetfori tape Vhavingia moisture-permeable back-- ing and a Apressure-sensitive adhesivewhich is; deposited from an aqueous dispersion, andinwhich the 'water-soluble portion is Vpositionedl towards the backing andfawayfrom the external; adhesive surface; to. obtain such a taper-,havingimproved bond between hydrophilic backings and adhesive by virtue ofthe presence of hydrophilic` colloidal agglutinant at and near .theinterface between adhesive and backing; toj avoid the usel of'hazardous and expensive Volatile organic solvents in the coating of.V pressure-sensitive adhesive Atapespand to-increase the eiciency of drying, equipment in terms. of square yards of tape or sheet material treated, by drying a double instead of a single web; Other objects aret' to rm up vthe coated pressure-sensitiveadhesive composition to the eucohesive stage by removal ofthe vehicle With'the adhesive out of contact with the atmosphere;to provide a coated composite web whichcan be handled without danger of contact of the adhesive with` any object to which it might become adherently attached; Vand to provide a method whereby prolonged heating or storage of the coated Web may safely be accomplished without loss of def sirable properties in the i'lnishedcoated sheet or tape. consideration of the specication as a whole;

-The method by which I obtain my novel result will now be explained more in detail by reference to the drawings; i

In the accompanying drawings: Figure rl is. a diagram showing an sensitive adhesive sheeting according to the present invention;

vFigure 2 represents theintermediate product before splitting; and n Figure 3 -represents a pressure-sensitive adhesive sheet material made according to the present invention.

Referring now to Figure 1 for a more detailedy description of an illustrative system adapted to themaking of adhesive sheet material or tape Otherobjects will be appreciated onv illustrativesystem for the continuous making of pressurev straining-tension to maintain smoothnessthereof,

from their respective supply rolls I3 and I4',Y

which are rotatably mounted in parallel spaced relation. The backings II and I2 are drawn be` tween squeeze rolls I5 andY IGVandtheaqueous dispersion of pressure-sensitive' adhesivev ITI? isifedf from the supply hopper I B through a suitable control Valve I 9 to the spreadinglioppersfi'lwherez it is evenly distributed between the two ba-ckingsr at the nip of the squeeze rolls, so asy to form a layer or lm of the aqueous dispersion between the backings as they are drawn through: the

.ilarly used in my novel process is the unied paper. backingdislosed by R. G. Drew in U. S.

Patent No. 2,236,527, which may consist of a creped toweling paper impregnated with a solution ofv broken-down'rubber, rosin, zinc oxide,

'and antioxidant, dried to remove the solvent, and

sizedon the-back surface with shellac. Such a sheetl is somewhat resistant to the passage of moisturevapor, .which will increase the time renip, thereby forming a composite web which `vcomprises the backings Ii and I2 with the* said lm between them. The squeeze rolls are adjustable so as to regulate the thickness of thev ln confined between the two backings. VThe compositeweb 20 is then drawn over guide rollsv 381' andi thence over a-plurality of steam' cans 36 where" the aqueous vehicle of. the dispersion is removed at an elevated temperature by migration through, and evaporation from, the backings toV formfthe dried lcompositeweb22, which is shown in detail inV Figure 2, and which comprises backings'II and I 2 with the interveninglayer 32V of pressurelsensitive adhesive. -The dried composite sheet; 22 while'still Warm is' passed between-the separating rolls 231'and. 24,where itis then sepa-'I rated `by drawing the two' backings II and I2, backV around theirrespective separating rolls 23 and? 24 and over their respective pull drums 25 and 26. The central adhesive layer 32 is thereby split along an approximateplane asindicated by the dotted line'v 29 of Figure 2, each of the backing's II and I2 beingv left coated with a portion (here shown as approximately half) of the thickness ofthe initial dried adhesive layer 32 to form the two pressure-sensitive adhesive sheets 21 and 28 respectively, Tension on the twoadhesivecoatedf sheets `2'! and 28, as applied thereto by the mechanically driven` pull drums and 26, is sufficient to overcome the restraining tension applied to the ba'ckings I I" and I2 at the supply' rolls I3 andy Il', to draw thefcomposite web 2li between the Squeeze rolls and over the steamv cans' and to split the'warm layer of dried adhesive.

The pressureesensitive adhesive' 'coated sheets or Webs 21 and 28 thus produced are drawn. from the pullv drums 25 and V26 by a' relatively light tension supplied by the wind-up rolls 30 and 3`I` respectively,A on which they are wound to form stock rolls which latter may subsequently be slit and wound intoA rolls of tape ready for use.

Figure 3 shows adhesive sheetY 28, one of the resultant adhesive sheets obtained on splitting the intermediate product 22 29, and xmiprising backing I2 and adhesive layer 34'. Said adhesive layer 34 ashere shown, represents approximately one-half of original adhesive layer 32.'- The exposed surface 331 of adlesive layer 34 is normally tacky and pressuresensitive. Y

As suitable moisture-permeable backings for use with water-dispersed pressures'ensitive ad# hs'ive compositions in my novel process I may use regenerated cellulose lmf(cellophane) untreated cloth, paper suitably unified with impregnating agents, or the like. VFor example, absorbent creped sulfate Kraft paper unied with ilexibilized glue, as described in U. S. Patent No. 1,760,820 issued to R; G. Drew may be used; or any other backing may be used which is sufficiently .moisturepermeable to permit removal of moisturefrom the adhesive through the backing,

and whichk has such other necessary qualifications along a central'plane`v lknown types' of .pressure-sensitive adhesivesl 4t# quired for drying of the composite web.

Where the resulting adhesive sheet is not to be placed against its own backing, but for example iste be kept in sheetform on allineror otherwise, an-untreated-brous backingmay conveniently be used; o1' aiibrous backingsuch as paper may be'lightly treatedrso as to increase-itsf.wet

strength withoutactually achieving unicationof the sheet; Such a backing mayadvantageous l'y be printed'or otherwise marked or decorated Where before' the application of the'l adhesive. untreatedpapers are used, they mustVA beso selected as to possess suicient resistanceto tearing or splitting so thatlthey will not failliii either of' these respects during the splitting ofthe-softened' adhesive layer. However; it is-possible to obtain at least partial' unilcationandA strengthening of` the untreated paper'by means vof the adhesive composition itself, as for example by the use of a'suiciently ii'uid dispersion whichwill-penetrate the paper as well as form the layer 32 of'dri'ed adhesive. Suitable sizing solutions maythen be appliedto the back sidev of the completedv tape after drying andv either before orafter splitting. The adhesiveY used' in Vmy process may consist of a rubber or reclaimed rubber and resin base type" of pressure-sensitive adhesive; or the base maybe a synthetic 4rubber fsuch 'as polyisobutylene, or a synthetic resinpolymer such as an alkyd resin made, for example, from castor oil and citric. acid'or any of the various -wellwhich are dispersible in'water may be used. 'Included also Vare pressure-#sensitive adhesives formdby emulsion polymerization oifsuitable4 monomeric substancesY or mixtures such as cerytain esters of acrylic ormethacrylic acid, vinyl acetate, and the like; for example,fmethyl acrylate, hexyl acrylate,l and. diallylsuccinate may bevinter-polymerized in emulsion form to produce. va suitable water-dispersed` pressure-sensitive adhesive. Partially reacted condensation or polymerization* type adhesives may be emp1oyed,

andthe reaction completed during Vor following the heating-and: drying of the coated composite `sheet and preferably prior to splitting. These u various adhesives are normally firm and coherent, but at elevated temperatures are sufiiciently` softened so that theymay be readilyv split.

The process of splitting: may best be accomplished-while the composite, after drying, is still at an elevatedA temperature, as disclosed above; or, for some adhesives, additional heat may be applied as by the use of internally heated separating rolls at 23 and 24 in Figure 1, or by enclosingA the separating rolls 23 and 24 within a heated oven, ori by p reheating the compositeweb by'lra'diation just prior to splitting, or by other means. The tape may if desired be Varticially cooled during its passage from the point of splitting to its pointof contact with the pull drum,

for example by passing through a blastof Vcold air, so as to be in the rm and coherent'statev before being wound up in roll form. Y

Another method of obtaining splitting of the adhesive layer which is contemplated' by me as a satisfactory alternative method of procedure, consists in the incorporation into the original adhesive of a small amount of an organic solvent or softener for the adhesive which is either less volatile or less readily removed from the adhesive mass than is the`water of the dispersion. Relaf tively small amounts of such solvent are sufficient to soften the adhesive mass suiiiciently so that it mayV Vreadily be split, particularly at slightly elevated temperatures, to form -two equally effective adhesive tapes when manipulated according to the method previously explained. The small amount of residual solvent remaining in the adhesive is readily removed, after the splitting operation has been performed, either by further brief heating or by exposure to` the atmosphere for a sufficient length of time before winding the coated sheet into roll form. K

` As a specific example of a water-dispersed pressure-sensitive adhesive suitable for use in the process of my invention, I may employ the following,- in which all parts are by weight.

VExample l Reclaimed rubber 1000 Antioxidant 5 Ester gum 200 Pure hydrocarbon thermoplastic terpene resin 110 Linseed oil free fatty acids 45 Casein solution f 190 Ammonium hydroxide (28% NH3) 45 Water f 800 In this formula, the reclaimed rubber may be a light gray carcass reclaim containing 50% rub-v ber hydrocarbon, having an kash content of 44.48% and a specific gravity of'1.3'7, such as produced by the Philadelphia RubberWorks, Akron, Ohio, under their designation No.. 6824 Reclaim. A condensation product of acetone andv aniline maybe used as the antioxidant; sucha product is obtainable from the Monsanto Chemi, cal Co. under the trade-name Flectol H. Pic colyte S-30 is a purev hydrocarbon thermoplastic terpene resin having a zero acid number and a softening point of about 30 C., sold by Pennsyl Vania Industrial Chemical Corp., of Clairton, Pennsylvania, and which is suitable for use 4in the above composition. The casein solution is made by dissolving 900 parts `of dry powdered casein in 2'700 parts of water to whicli-90 parts of penta-chlor lphenol (such as Dowicide G,

obtained from the Dow Chemical Co.) may be' added as a preservative, solution being obtained by the addition to the casein-and-water slurryv of 45 parts of ammonium hydroxide containing; 28% NH3.

In preparing the water-dispersed adhesive, the* anti-oxidant is first milled into the reclaimedrubber. To this are then added the resinousconstituents, the oil acids, and finally the casein solution, mixing being accomplished in a heavyduty internal mixer. Theammonium hydroxide is then slowly added, followed by the Water. Inversion to an oil-in-water type emulsionis obtained after the addition of a minor proportionv of the water; the balance of the water may then be added more rapidly to dilute the mix to av usable viscosity.

In place of all or part of the casein, various Ll U other hydrophiliccolloidal agglutinants maybe used: 'examples are polyvinyl'alcohol, isinglass. gelatine, soy bean proteinglues, Mazein (corn prolamine), dextrin, kmethyl cellulose, water#- soluble polyhydric-alcohol/polybasic-acid resin, urea-aldehyde resin, water-soluble alkyd Aresin salt, or mixtures thereof. These materials act as protective colloids and assist in forming the dispersion; in additionythey afford a means of obtaining' a rm bond to hydrophilic moisture permeable backings.

The water-dispersed adhesive of the foregoin example was coated between two webs of creped kraft paper previously unified with glycerine- .plasticized glue, in a thickness sufficient to provide a total of 40-48 grains of dry adhesive per 24 square inches of the composite. After drying at F., it was split at the same temperature. cooled slightly, and wound up to produce two finished rolls of pressure-sensitive adhesive tape; When slit into narrow widths and tested, this tape showed satisfactory adhesion to various surfaces and'was suitable for use as a masking tape. When a` single coat of the same dispersed adhesive, to the extent of 20-24 grains-per 24 square inches, (dry weight), was applied to a single webof the same type of backing and dried at 160, the exposed dried surface was found to be almost entirelytack-free. v

During the evaporation of the water from the composite web, it seems likely that soluble vmaterials such as soap, and the casein or other protec-v tive colloid when present in the dispersion,"are carried to the pervious backing and may evenbe carried to the evaporative outer surface. A concentration of Water-soluble materialsmust there-v by take place at or in the backing, and this must result in a concentration of water-insoluble and adhesive materials in the center layer. Thisgradation of soluble and insoluble materials may be the explanation of the improved adhesion of the adhesive surface to other surfaces, and also the highly satisfactory bond between adhesive layer and hydrophilic treated backing, which are obtained by my novel process.

By maintaining equal tension on the pull drums 25 and 26, and thereby maintaining equal angles between each of the pressure-sensitive adhesive sheets 21 and 28 and the composite web22 as the adhesive layer is split, and also by carefully controlling the distribution of temperature within said composite web 22, it is possible to obtain essentially equal weights of adhesive on each of the said sheets 21 and-28. Where backings Il and I2 are of identical construction, and where there is to be produced but a single type of ad# hesive sheet, the above-named conditions are desirable. Splitting of the adhesive along a plane located toward either side of the central plane l shown in Figure 2 may, however, be obtained when desired, for example by differential heating or cooling of the two surfaces of composite web 22 so asto provide a plane at maximum temperature whichis removed from the central plane, or by unequal tension applied by the pull drums 25 and 26, or by vuse of dissimilar backings which for example are of different thickness.

As previously indicated, the composite web 22 may be split by direct application of tension and without the use of the separating rolls 23 and 24' of, Figure 1. Such an arrangement usually requires the web to be moved forward by additional driving means; for example, one or more chanically driven. 1

-It will oi?l course1be-obvious that the Vcoating and drying operation,andthe splitting4 operation, may beaccomplished separately. r-Ihus `thecomposite web 22 may vbe v`wound upJ in a roll for temporary storage, and rmay 'latergbe unwound, reheated as by oneof the methods Apreviously indicated, and split.

The freshly exposed 'adhesive 'surfaces formed on splitting adhesivelayerS-Z of Figure 2, such as vthe surface33 in Figure 3, are ordinarily fnt smooth; but their contact undertensionwith the smooth surfaces of the fpulldrums 25or Zlfand the further pressure of :the: adhesive against the outer-surface of the backing when-the vtape 4isvin roll form, frequently makes theadhesiyesurface appreciably smoother than `it was immediately after the vsplitting operation. V

Heating on steam vcans has been disclosed in connection with Figure 1 as a method-of removing the -volatile vehicle -from the composite 'coated sheet.V Where Vthe backing carries 1a Athermoplastic backsize, for-example the shellac backsize of they paper backing of the Drew Patent No. 2,236,527 previously mentionedfit may be necessary Yto avoid contact of the backing with hot metal surfaces; in such cases, and also 'under various other conditions, it may be desirable to dry the composite'sheet Vin anoven. The sheet may be suspended in loops, in which casean addiv tional pull drum maybe found necessary lto fpull the sheet through the squeezerolls; or it .maybe passed through the -oven under continuous slight tension and in single -or multiple pass.v Y

While thek water-dispersed'adhesive is conveniently applied by the method shown in Fig-ure 11 and previously described, it may lalso be l.applied in any of several other 'known methodsso vlong as all, or essentially all, of the evaporation of water is allowed to take place through-the porous back-- ing and not from the exposedadhesive surface. For example, a filmV of dispersed adhesive maybe laid on each backing member separately, andthe two combined to form the composite; or the adhesive may be applied to vbut one of the backing members, and subsequently covered withthe other member prior to evaporation of solvent. While the use of squeeze rolls -is desirabla'other neaiis of coating or spreading the `dispersed adhesive and of forming the composite web 2t maybeemployed; for example, spreader bars 'may be used.

There is thus provided a new method for the production of pressure-sensitive adhesive vsheets or tapes, in which the pressure-sensitive rcornposition is rmed up from the initial 'fluid coatable state to, or nearly to, the nal desired 'rin and coherent state while 'held between kt'wo backing members, which are later separated under conditions such` that the adhesive layer Vis centrally split to provide on each of said baokings'a coating, having a freshly exposed and fully adhesive surface, of normally tacky and -pressuresehsitve adhesive. By this method, Vadhesive compositions which contain mobile tackiness-reducing Vsubstances may be made to provide Vfull adhesin value. Likewise, adhesive compositions which 'are subject to oxidation by air at elevated 'temperatures to non-tacky products may safely Vrbe subjected to such temperatures during 'the rming operation without loss of tack. Combinations of backings and adhesive compositions vmay be' used which, if combined by previously-'known methods, would result in badly curled, broken, stretched, or otherwise deformed and 'useless coated products. Furthermore, a method is provided ffholdng pressure-sensitive adhesive coated bacliiirigs 1in storageforlong periods of time without deterioration of the adhesive surface by surface oxidation, collection of dust, -or thelike, and without any necessity -for the use of a removable liner o1' slip-sheet. Y ,Y

What I claim is as follows: o o o l. In a method of making normally tacky and pressureesensitive'adhesive sheets and tapes, the steps comprising applying an intercalated layer of an-aqueous dispersion of water-insoluble normally tacky pressure-sensitive adhesive composition containing a hydrophilic colloidal agglutinant between. two moisture-permeable ilexible tape backing members, removing the aqueous vehicle through and from the exposed surfaces of-s'aid backing members, and splitting the dried layer of adhesive.

Y 2. In a method of making normally tacky and pressure-sensitive adhesive sheets-and tapes, the steps comprising applying an intercalated layer of an aqueous dispersion of water-insoluble normally tacky pressure-sensitive adhesive compositionrcontaining a hydrophilic colloidal agglutinant between two vhydrophilic moisture-permeable iiexible tape backingmembers, removing the aqueous vehicle through and from :the exposed surfaces of said 'backing members, and splitting the dried layer of adhesive.

8i `In a method of making normally tacky and pressure-sensitive adhesive sheets and tapes,`the steps comprising applying an intercalated layer of an aqueous dispersionfof lwater-insoluble normally tacky pressure-sensitive adhesive, composition containing a hydrophilic colloidal vagglutinant between two moisture-permeable ilexible tape backing members, removing the aqueous vehicle by evaporation from Athe exposed outer surfaces of said backing members, and splitting the 'dried layer of adhesive at an elevated temperature, said adhesive being of a type which softens on heating, A

4.',In a vmethod of makingfnormally tacky and pressuree'sen'sitive adhesive sheets and tapes', the steps `corriprisirigl applying an intercalated layer of van aqueousdispersion of water-insoluble 'normally ltacky vpress'ure-sensitive adhesive compositionfloont'aining a hydrophilic colloidal agglutinant between two uniiied paper moisture-permeable `exible tape backing members, removing the aqueous vehicle through and from the exposed surzuesv of said backing members, and splitting the dried layer of adhesive.

5. In a method of making normally tacky and pressure-sensitive adhesive sheets and tapes, the steps comprising` applying an intercalated layer of an aqueous dispersion of wateririsoluble normally tacky pressure-sensitive adhesive compositin, 'containing a hydrophilic colloidal agglutinant Yand a rsmall amount of an organic solvent, between vtwo moisture-permeable exible tape backing members, removing the aqueous vehicle through and from the exposed surfaces of said backing members'splitting the resulting adhesive layer, and removing the organic solvent by subsequent evaporation. y A

` WILFRED J. MOI-IR.

REFERENCES CITED The v:following referefhlces are of record in the file of this patent: 4

UNITED VS'IAI'Eil PATENTS Name Date Angieret al. O'ct. 1'8, 1'9'3'2 Number 

